WO2001057117A1 - Selbstverstärkendes, thermoplastisch verformbares halbzeug, insbesondere für die herstellung von sanitärartikeln, verfahren zur herstellung sowie daraus hergestellte formkörper - Google Patents

Selbstverstärkendes, thermoplastisch verformbares halbzeug, insbesondere für die herstellung von sanitärartikeln, verfahren zur herstellung sowie daraus hergestellte formkörper Download PDF

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Publication number
WO2001057117A1
WO2001057117A1 PCT/EP2001/000489 EP0100489W WO0157117A1 WO 2001057117 A1 WO2001057117 A1 WO 2001057117A1 EP 0100489 W EP0100489 W EP 0100489W WO 0157117 A1 WO0157117 A1 WO 0157117A1
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WO
WIPO (PCT)
Prior art keywords
semi
weight
meth
finished product
acrylate
Prior art date
Application number
PCT/EP2001/000489
Other languages
German (de)
English (en)
French (fr)
Inventor
Egbert Schöla
Gerald Molnar
Robert Schwenninger
Original Assignee
Röhm GmbH & Co. KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Röhm GmbH & Co. KG filed Critical Röhm GmbH & Co. KG
Priority to EP01909640A priority Critical patent/EP1210385B1/de
Priority to AU37310/01A priority patent/AU3731001A/en
Priority to US09/926,249 priority patent/US6699544B2/en
Priority to DE50109287T priority patent/DE50109287D1/de
Priority to JP2001557945A priority patent/JP2003522240A/ja
Publication of WO2001057117A1 publication Critical patent/WO2001057117A1/de

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/007—Using fluid under pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
    • B29C35/045—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using gas or flames
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/10—Forming by pressure difference, e.g. vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/769—Sanitary equipment
    • B29L2031/7696—Showers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • thermoplastically deformable semi-finished product especially for the production of sanitary articles
  • the present invention relates to plate-shaped semi-finished products made of filled poly (meth) acrylate, processes for producing such poly (meth) acrylate plates, and moldings, preferably sanitary articles, which can be produced from the semi-finished product.
  • the present invention relates to self-reinforcing, thermoplastically deformable semifinished product, consisting of a single-layer plate made of filled poly (meth) acrylate, the semifinished plate product having an average filler content F m in weight percent based on its total weight, an upper side 0 and a lower side U.
  • This semi-finished product made of poly (meth) acrylate is used in particular for the production of sanitary articles, such as bathtubs, shower trays and sinks, preferably with a view to shower trays and sinks in
  • High-performance deformation process such as the deep-drawing process.
  • sanitary articles made of poly (meth) acrylate (“acrylic glass”) are manufactured in a multi-stage manufacturing process. First, an acrylic glass plate is produced, which is then thermoformed. Because of the inadequate mechanical properties of the molded body, reinforcement must be provided. This is done, for example, by Spraying and curing a polymerizable reactive resin (styrene / glass fiber chaff
  • Reinforcement materials also do not have fibers (glass fiber chopped) lying flat on the back of the sanitary article rolled on by hand.
  • the reinforcing layer consists of a cold-curing (meth) acrylate resin which has a content of 1 to 75 percent by weight of fine fillers with a particle size of not more than 100 ⁇ .
  • a cold-curing (meth) acrylate resin which has a content of 1 to 75 percent by weight of fine fillers with a particle size of not more than 100 ⁇ .
  • WO 97/46625 PCT / GB97 / 01523 (ICI) proposes to reduce the risk to the working and operating personnel by using aqueous redox systems to harden the (meth) acrylate system to be sprayed on. Although this reduces the impairment caused by solvents (ethyl methyl ketone, other ketones, organic solvents and the like) during the spraying process, the spray application itself is not a completely free process. For example, the finest distribution of comparatively volatile polymerizable constituents of the (meth) acrylate resin, which is unavoidable when spraying, must be mentioned. The relatively low MAK values for MMA and other monomers are achieved much faster when spraying than with other processing methods. It would be particularly desirable to be able to dispense with the subsequent spraying or application of a reinforcing layer.
  • solvents ethyl methyl ketone, other ketones, organic solvents and the like
  • the task of the invention was to create fully recyclable reinforced sheets made of poly (meth) acrylate (“acrylic glass sheets”).
  • Another object of the invention is to provide fully recyclable moldings, such as preferably shower trays or wash basins, which can be completely recycled using metal baths, in particular using the depolymerization technology known per se for acrylic glass, and as far as possible without endangering the operating personnel.
  • Another object of the invention is to be seen in providing plate-shaped semi-finished products from which sanitary articles, such as shower trays or preferably
  • Wash basins can be produced which, with the greatest possible material savings, meet the general requirements as they are placed on such sanitary articles with regard to stability.
  • Poly (meth) acrylate sheets represent a particular danger, being pushed back as far as possible.
  • Another task is to provide an impact-resistant semi-finished product in the form of a poly (meth) acrylate plate.
  • both the new semi-finished product and the new sanitary article that can be produced from it should be as simple as possible to manufacture.
  • a sanitary article made of reinforced poly (meth) acrylate panels which high and / or improved values with regard to one, several or all of the mechanical parameters such as tear resistance, bending strength (measured on the inside (top) of the acrylic glass molding), bending strength (measured on the back (underside)), modulus of elasticity, impact resistance (measured on the Side of the acrylic glass molded part, inside or on the top), impact resistance (on the back (corresponds to
  • a self-reinforcing, thermoplastic deformable semi-finished product in particular for the production of Sanitary articles, preferably in the deep-drawing process, consisting of a single-layer plate made of filled poly (meth) acrylate, the semi-finished plate having an average filler content F m in weight percent based on its total weight, an upper part e 0 and a lower side U, which is characterized by that the semi-finished sheet is depleted of fillers on the top 0 and enriched on the underside U, based in each case on F m , it is possible to provide a semi-finished product from which, for example by simple thermoforming processes, sanitary articles can be produced, which meet all the requirements set by the standard institutes and industrial processors with regard to the physical properties of the sanitary article in an outstanding manner and which at the same time permit a greatly simplified production of sanitary articles.
  • a large number of additional advantages can be achieved.
  • the semifinished product according to the invention is "self-reinforcing", whereby for the first time a semifinished product in sanitary quality is provided, from which a suitable sanitary article, preferably a shower tray or wash basin, can only be produced by thermal shaping.
  • additional reinforcement refers to the improvement of mechanical properties of a single-layer plate by means of an additional layer.
  • the additional layer can be laminated to the plate, either with or without an adhesion promoter, or it can, for example, also have a reinforcing effect
  • the reinforcing effect can be achieved, for example, by the modulus of elasticity
  • DIN 53 457 can be determined. Any increase in the modulus of elasticity of the reinforced plate compared to the plate without an additional layer is to be regarded as a reinforcement.
  • Frled poly (meth) acrylate means a poly (meth) acrylate which has fillers.
  • “semifinished product” means a plate-shaped intermediate product made from filled poly (meth) acrylate and intended for further processing
  • Pre-products are manufactured by post-production processes (preferably thermal forming, particularly preferably high-performance deformations such as deep drawing), finished products (sanitary articles) of any shape u. Dimensions made.
  • plates is to be understood to mean flat structures of any geometry, which can be shaped, for example, round, square, semicircular or in some other way.
  • the plates are preferably square or rectangular.
  • the “top 0” of the semi-finished sheet according to the invention denotes the surface of the inside of the sanitary article obtainable from the semi-finished product by molding.
  • the inside of the sanitary article is the side that comes into regular contact with water when used properly, that is to say in tubs, cups or basins the inside.
  • the “underside U” of the semi-finished product according to the invention denotes the surface of the outside of the sanitary article obtainable from the semi-finished product.
  • the outside of the sanitary article is the side that does not regularly come into contact with water when used as intended.
  • the “average filler content F m ” of the semi-finished sheet results from the ratio of the weight of the fillers contained in the semi-finished sheet to the total weight of the semi-finished sheet multiplied by a factor of 100.
  • the filler content F m is advantageously in the range between 20 and 80 percent by weight , preferably between 30 and 70 percent by weight, particularly expediently between 40 and 60 percent by weight
  • the amount of the filler contained in the semifinished product of the invention can significantly control the mechanical properties.
  • the semi-finished sheet is depleted of fillers on the top 0 and enriched on fillers U, based in each case on F m . Depleted means that the local content of fillers in the area of the top is less than F m , while enriched means that the local content of fillers in the area of the bottom is greater than F m .
  • “Local content of fillers” means the filler concentration in a unit volume element determined in [kg-m -3 ]. The depletion of fillers in the area of the top of the semi-finished product makes it particularly expedient to provide a high-gloss surface, while the enrichment of the fillers in the area of Bottom of the semi-finished product is particularly favorable for the reinforcing effect.
  • semi-finished products which are characterized by a thickness d which, viewed in cross-section with respect to the semi-finished product, extends from the top 0 towards the bottom U, so that d at 0 has the value zero and d at U has the value l »d, where an average filler content F 0 in percent by weight, based on the section of the semi-finished sheet between 0 and 0, l» d, is less than F m , while an average filler content F y in percent by weight, based on the section of the semi-finished sheet between 0.9 «d and l « d, greater than F m .
  • Fo is determined analogously to F m , but for a layer close to the top with a defined thickness.
  • Fu is determined for a layer close to the underside of the semi-finished product with a defined thickness.
  • the distribution of the filler in the semi-finished product can be any distribution of the filler in the semi-finished product.
  • the gradient of the filler is expediently not continuous, but discontinuous.
  • the semi-finished product according to the invention is therefore characterized by a discontinuous gradient of the filler concentration running from 0 to U (inconsistent change with increasing thickness of the plate). In this way, for example, certain particularly stressed problem areas of sanitary articles can be reinforced.
  • the type, shape and amount of the fillers contained in the sheet-like semi-finished product can be varied over a wide range, depending on the particular intended use.
  • the fillers which can advantageously be used in the production of the self-reinforcing semi-finished product include talc, dolomite, natural Adhesions of talc and dolomite, mica, quartz, chlorite, aluminum oxide, aluminum hydroxide, clays, silicon dioxide, silicates, carbonates, phosphates, sulfates, sulfides, oxides, metal oxides, glass powder, glass beads, ceramics, kaolin, porcelain, cristobalite, field slit, chalk, Carbon and / or hollow microparticles filled with inert gas.
  • silanized types of fillers are also preferred, since better matrix adhesion can be achieved by silanization compared to fillers that are not silanized.
  • Microparticles can be used. Basically, they are hollow particles which can be regular or irregular, but which are preferably spherical or spherical and have inert gas in their cavity.
  • micro hollow spheres that can be used basically include
  • Hollow microspheres made from different materials such as glass, metals, metal oxides, polymers and organic compounds.
  • Hollow plastic spheres made of polymers such as polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylate, polyacrylonitrile, polybutadiene, polyethylene terephthalate, are preferably used for the invention.
  • Examples of such polymers and copolymers which form the hollow spheres themselves include vinylidene chloride-acrylonitrile copolymer,
  • Mixtures of hollow microspheres can preferably also be used within the scope of the invention.
  • the hollow microspheres or microparticles which can be used according to the invention can be coated with coatings in order to adapt the processing properties or to vary the reinforcing properties.
  • Modifications from simple hollow microspheres are also particularly suitable.
  • those hollow microspheres which consist of polymers which are coated with mineral substances in order to ensure better stability against the influence of the surrounding medium.
  • the coating of the hollow microspheres can be made from very fine-grained minerals such as Calcium carbonate,
  • Quartz, mica, aluminum hydroxide, cristobalite and the like are made.
  • Hollow microspheres are particularly preferred, especially those made of plastic, which are coated with calcium carbonate.
  • An overview of the manufacture of hollow microspheres can be found, for example, in Mat. Res. Soc. Symp. Proc. Vol. 372, 1995 Materials Research Society by David L. Wilcox, Sr. and Morris Berg, pages 3 to 13, and the literature cited therein.
  • gas-filled hollow microspheres made of plastic include ® Dualite types, for example ® Dualite M 6032, (Pierce & Stevens Corp.); ® Expancel types, for example ® Expancel 642 WU, ® Ropaque types, for example ® Ropaque OP 62 (Rohm and Haas Co.), Matsumoto Microsphere, for example Microsphere F-30E (Matsumoto Yushi Seiyaku Co. Ltd.) and the like.
  • ® Dualite types for example ® Dualite M 6032, (Pierce & Stevens Corp.)
  • ® Expancel types for example ® Expancel 642 WU
  • ® Ropaque types for example ® Ropaque OP 62 (Rohm and Haas Co.)
  • Matsumoto Microsphere for example Microsphere F-30E (Matsumoto Yushi Seiyaku Co. Ltd.) and the like.
  • the filler types mentioned can have different morphologies. They can be spherical or aspherical, with fibrous or splintered fillers being less preferred. Advantageous self-reinforcing semi-finished products with particularly good combinations of properties are obtained when the reinforcing fillers contained have a platelet-like or needle-like shape. Spherical and in particular platelet-shaped or needle-like fillers enable the particles to be aligned along the shape of the semifinished product into sanitary articles, for example by high-performance deformation processes such as deep-drawing the semifinished product
  • This orientation of the reinforcing filler particles preferably parallel to the surface of the plate-shaped semi-finished product, can ensure a balanced stiffness-impact resistance ratio in the sanitary article resulting from shaping, enables a good surface quality of the sanitary article, ensures sufficient flow seam strength, and can maintain the heat resistance improve and generally has a positive influence on the feel of the finished sanitary ware.
  • a special embodiment of the semifinished product resulting according to the invention is present when the filler particles used are layer fillers.
  • the size of the filler particles can also play a role in the quality of the semi-finished product according to the invention.
  • the stiffness of the semi-finished product and thus the resulting sanitary article can be controlled by a suitable size of the fillers.
  • the reinforcing fillers are generally used in the grain size range from approximately 0.01 to approximately 100 ⁇ m.
  • the average particle size of the filler used is expedient in the range from 0.01 to 80 ⁇ m, in particular in the range from 0.05 to 30 ⁇ m, very particularly expedient in the range from 0.1 to 20 ⁇ m.
  • the residue of the fillers used is less than two percent by weight with a 20 ⁇ m sieving.
  • the thickness of the semi-finished panels is variable. So both thicker and thinner self-reinforcing semi-finished products belong to the invention. Because of the associated
  • the thickness d of the Semi-finished product in the range of 1.5 to 12 mm, preferably 2 to 10 mm, particularly preferably 4 to 8 mm, even more preferably 4.5 to 7 mm.
  • the semifinished products according to the invention are, for example, by polymerization of a (meth) acrylate system in one
  • the semifinished product according to the invention is preferably obtainable by polymerizing a (meth) acrylate system which has a viscosity in the range from 0.02 to 0.1 Pa »s (20 to 100 cP), preferably 0.03 to 0.08, before the polymerization Pa »s (30 to 80 cP), particularly preferably 0.04 to 0.06 Pa » s (40 to 60 cP), very particularly advantageously about 0.05 Pa »s (50 cP).
  • the invention therefore also includes a method for
  • a plate-shaped semi-finished product in which a) a polymerizable, filled (meth) acrylate composition is provided, b) the composition provided is poured into a prepared mold, c) the composition is polymerized in the mold at a temperature above room temperature to obtain a plate-like semi-finished product, and d) the semi-finished product is removed from the mold,
  • the viscosity of the polymerizable, highly filled '(meth) acrylate composition before the polymerization in the mold to a value in the range from 0.02 to 0.1 Pa-s (20 to 100 cP), preferably 0.03 to 0 , 08 Pa-s (30 to 80 cP), particularly preferably 0.04 to 0.06 Pa »s (40 to 60 cP), very particularly suitably about 0.05 Pa-s (about 50 cP).
  • Weight ratio of (pre) polymer to polymerizable monomers in the composition regulated.
  • Viscosity adjusting agents regulated Such viscosity adjusting, i.e. regulating agents are known per se to the person skilled in the art. These include, for example, ionic, nonionic and zwitterionic emulsifiers.
  • the composition includes the following measures:
  • the viscosity of the polymerization system can be varied by adding a regulator.
  • wetting agent additives such as the lecithin mentioned or ® Catafor and the like, can enable the viscosity to be adjusted to the desired value.
  • the filler concentration as such influences the viscosity of the polymerization system, as does the type of filler or filler mixture (grain size, oil number, surface treatment).
  • thixotropic agents for example ® Aerosile
  • Viscosity can change the viscosity of the polymerization system.
  • the viscosity of the system can be influenced via the polymerization temperature.
  • the initiator concentration and the kinetics of the polymerization reaction can also influence the viscosity of the polymerization system and thus the degree of sedimentation of the fillers.
  • the semifinished products according to the invention can be molded using known thermoplastic molding processes.
  • the invention therefore also includes moldings made from a semifinished sheet described herein.
  • the shaped body according to the invention is characterized in that the shaped body is a sanitary article, produced by thermoplastic shaping of a semi-finished plate.
  • sanitary articles include, among other things, basins, certain shapes of tubs, cups and similar shapes, which can also be irregular.
  • shower trays and wash basins are particularly preferred.
  • a special embodiment of the invention comprises molded articles which are characterized in that the molded article is a shower tray, produced by deep-drawing a semi-finished plate.
  • the semi-finished products according to the invention are semi-finished poly (meth) acrylate products. These are characterized by a high, preferably predominant, ie relatively high content of 50 percent by weight or more of poly (meth) acrylates.
  • Poly (meth) acrylates are polymers which are believed to have structural units of the formula (I)
  • C ⁇ _g-alkyl includes the residues mentioned in C ⁇ _ 4 ⁇ alkyl and additionally residues with 5 or 6 carbon atoms, such as preferably 1-pentyl, 2-pentyl, 3-pentyl, 2, 2-dimethyl-1-propyl, 3-methyl-1 -butyl, 3-methyl-2-butyl, 2-methyl-2-butyl, 2-methyl-1-butyl, 1-hexyl.
  • Exemplary compounds which have the aforementioned structural unit include, among others, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polypropyl acrylate, polybutyl acrylate, polypropyl methacrylate, polybutyl methacrylate and copolymers which have two or more of these types of polymers.
  • the first four compounds are preferred in the context of the invention.
  • Polymethyl methacrylate (PMMA) is very particularly preferred.
  • poly (meth) acrylate plates can also be used within the scope of the invention from copolymers which contain up to 50% by weight of at least one further vinylically unsaturated monomer which can be copolymerized with at least one substituted or unsubstituted acrylic ester monomer.
  • Examples include: a. Methyl methacrylate-styrene copolymers or methyl methacrylate-butyl acrylate-styrene terpolymers.
  • the comonomers are optional constituents or components, which are preferably contained in a minor amount in the form of copolymers containing them in acrylic glass. You will be in the Usually selected so that they have no adverse effect on the properties of the poly (meth) acrylate to be used according to the invention.
  • the color reduction of the copolymer can, for example, particularly preferably by using an electron-rich
  • Monomers such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstryrene can be achieved.
  • the semifinished product according to the invention or the poly (meth) acrylate plate according to the invention can have conventional additives.
  • additives include, among other things, antistatic agents,
  • fillers which are inert under the conditions of the depolymerization of the poly (meth) acrylates are understood to mean those substances which depolymerize the
  • Methyl methacrylate (MMA) by thermal treatment of acrylic glass waste at temperatures> 200 ° C, condensation of the resulting monomer vapors and processing of the crude monomers in the literature and in the patents various continuous and discontinuous Procedures described.
  • the polymer material is placed in a boiler, which is partially filled with lead and is heated from the outside. At temperatures above 400 ° C, the polymer material depolymerizes and the resulting monomer vapors are piped into a condenser, where they are condensed into a crude, liquid monomer.
  • a boiler which is partially filled with lead and is heated from the outside.
  • the polymer material depolymerizes and the resulting monomer vapors are piped into a condenser, where they are condensed into a crude, liquid monomer.
  • Depolymerization processes are known for example from DE-OS 21 32 716.
  • the semifinished products according to the invention can be obtained, for example, by polymerizing a (meth) acrylate system in a casting process, preferably by the chamber process, roster process or other variants and modifications of the chamber process, the polymerizable process
  • Component A) is an essential component of the (meth) acrylate system to be polymerized.
  • a component in parentheses stands for its optional usability, i. H. (Meth) acrylate stands for acrylate and / or methacrylate.
  • the monomer component A) contains at least 50% by weight of (meth) acrylate, monovalent (meth) acrylates with a C ] _-C4 ester radical being preferred. Longer chain esters, ie those with a C5 or longer chain ester residue are limited to 50% by weight in component A).
  • Component A) preferably contains at least 40 percent by weight of methyl methacrylate.
  • component A) may also contain other co onomers, the proportion of which is limited to 50% by weight.
  • vinyl aromatics and / or vinyl esters can each contain up to 50% by weight in component A). Higher proportions of vinyl aromatics are difficult to polymerize in and can lead to segregation of the system. Higher proportions of vinyl esters can continue to cure insufficiently at low temperatures and tend to shrink more.
  • Component A) is preferably composed of 80-100% by weight and particularly preferably 90-100% by weight of (meth) acrylates, since semi-finished products with processing and usage properties favorable for sanitary articles can be achieved with these monomers.
  • Acrylates the proportion of C 2 -C 4 ⁇ esters in (meth) is preferably limited to 50 wt .-% in component A), these esters are preferably max. 30% by weight and particularly advantageous at max. Contain 20% by weight in component A). This makes it possible to build up particularly flexible layers.
  • Suitable monofunctional (meth) acrylates are in particular methyl methacrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl triglycol methacrylate, hydroxypropyl methacrylate.
  • Particularly suitable comonomers are vinyl toluene, styrene and vinyl esters.
  • Styrene is preferably limited to max. 20 wt .-% in A) limited, because a higher content to disturb the
  • Component A) also essentially contains polyvalent (meth) acrylates.
  • the polyvalent (meth) acrylates Contribute through their cross-linking effect during the polymerization, among other things, to reducing the water absorption of the semi-finished product and thus the ultimately resulting sanitary article.
  • Polyvalent (meth) acrylates are preferably present in the (meth) acrylate system in component A) in an amount of 0.1-30% by weight, particularly advantageously in an amount of 0.2-5% by weight.
  • the polyfunctional (polyvalent) (meth) acrylates are used to link polymers between linear molecules. Properties such as flexibility, scratch resistance, glass transition temperature, melting point or hardening processes can be influenced.
  • Multi-functional (meth) acrylates that can preferably be used include:
  • R is hydrogen or methyl and n is a positive integer between 3 and 20, such as.
  • R is hydrogen or methyl and n is a positive integer between 1 and 14, such as.
  • Preferred common polyfunctional (meth) acrylates include, among others, triethylene glycol dimethacrylate (TEDMA), trimethylolpropane trimethacrylate (TRIM), 1,4-butanediol dimethacrylate (1,4-BDMA), ethylene glycol dimethacrylate (EDMA).
  • TEDMA triethylene glycol dimethacrylate
  • TOM trimethylolpropane trimethacrylate
  • 1,4-BDMA 1,4-butanediol dimethacrylate
  • EDMA ethylene glycol dimethacrylate
  • a (meth) acrylate system to be used according to the invention are polyvalent (at least double-functional) urethane (meth) acrylates.
  • Particularly useful layers are obtained when certain new types of urethane (meth) acrylates are used.
  • hydroxyalkyl (meth) acrylic esters with polyisocyanates and polyoxyalkylenes which have at least three hydroxyl functionalities, the proportion of polyethylene oxide being less than 50% by weight, based on the total amount of polyoxyalkylene.
  • Hydroxyalkyl (meth) acrylic acid esters which can be used according to the invention are esters of (meth) acrylic acid with dihydric, aliphatic alcohols. These connections are well known in the art. They can be obtained, for example, by the reaction of (meth) acrylic acid with oxiranes.
  • Butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and glycidyl ester These compounds can be used both individually and as a mixture.
  • the conversion to the hydroxyalkyl (meth) acrylic acid esters is described, for example, in DE-A-24 39 352, DE-15 68 838 and GB 1 308 250.
  • hydroxyalkyl (meth) acrylic acid esters thus obtainable are frequently commercially available and are therefore particularly suitable for the purposes according to the invention.
  • the hydroxyalkyl (meth) acrylic acid esters can also contain substituents, such as phenyl radicals or amino groups.
  • the hydroxyalkyl radical of the ester can also contain polyoxyalkylene groups, which can be both linear and branched, such as, for example, polyethylene oxide, polypropylene oxide and polytetramethylene oxide. These groups often have between 2 and 10 oxyalkylene units.
  • Preferred hydroxyalkyl (meth) acrylic acid esters include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl ethacrylate,
  • polyisocyanates refer to low molecular weight compounds which contain two or more isocyanate groups in the molecule.
  • the proportion of polyisocyanates with 3 or more isocyanate groups By selecting the proportion of polyisocyanates with 3 or more isocyanate groups, the property spectrum of elongation at break and tensile strength can be influenced in a targeted manner. The higher the proportion of connections with three or more
  • the polyisocyanates which can be used in the present invention include, inter alia, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4, 4'-dicyclohexyldiisocyanate, meta- and para-tetramethyl-xylene diisocyanate, 3 -Isocyanatomethyl-3, 5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), hexamethylene diisocyanate, 1, 5-naphthylene diisocyanate, dianisidine diisocyanate, di (2-isocyanatoethyl) - bicyclo [2.2.1] -hept-5-en-2, 3-dicarboxylate, 2,2,4- and
  • Suitable polyisocyanates can also be obtained, for example, by reacting polyhydric alcohols with diisocyanates or by polymerizing diisocyanates. It is also possible to use polyisocyanates which can be prepared by reacting hexamethylene diisocyanate with small amounts of water. These products contain biuret groups.
  • polyisocyanate is isophorone diisocyanate.
  • the analog isothiocyanates are also suitable as polyisocyanates in the context of the present invention. This one but are less commercially available, these compounds are less preferred.
  • Polyoxyalkylenes which have at least three hydroxy functionalities can be obtained, for example, by polyaddition of cyclic ethers, such as, for example, oxiranes and tetrahydrofuran.
  • the oxiranes that can be used for polyaddition include those mentioned above. Of these, propylene oxide is preferred.
  • alcohols can be used, for example, as starting molecules that have at least three hydroxyl groups.
  • polyoxyalkylenes which have three or more hydroxy functionalities can also be prepared in situ. This is achieved by variant B) in that polyoxyalkylenes with two hydroxy functionalities are linked by polyisocyanates with three or more isocyanate groups.
  • the weight average molecular weight of the polyoxyalkylenes can vary within wide limits. It is preferably in the range from 2,000 to 20,000, preferably in the range from 4,000 to 10,000 and very particularly preferably in the range from 4,000 to 8,000 g / mol. It is essential, however, that the polyether chains induce a minimum of flexibility. Accordingly, the chain length of the polyether chains should on average be greater than 10 units, preferably greater than 20 units and very preferably greater than 30 units.
  • cyclic ethers can also be used as a mixture, resulting in copolymers.
  • Block copolymers of this type can also be used.
  • Hydroxy functionalities are commercially available.
  • Preferred polyoxyalkylenes are polyoxypropylenes.
  • Polytetramethylene oxides which can be used together with the polyoxypropylenes can also be preferred, these polyoxyalkylenes each having at least three reactive, terminal hydroxyl functionalities.
  • R 1 is hydrogen or methyl
  • R 2 is a linear or branched alkylene group with 2 to 20 carbon atoms or alkylene oxides with 4 to 50 carbon atoms,
  • R 3 represents an aromatic, aliphatic or cycloaliphatic group containing up to 18 carbon atoms, which are derived from diisocyanates or diisocyanate mixtures
  • R 4 represents an alkylene radical having at least 2 carbon atoms, provided that at least half of all R 4 radicals in the uretha (meth) acrylate of the formula (I) have 3 or more carbon atoms
  • n an integer> 10,
  • Z is a connecting group derived from alcohols with at least three hydroxyl groups or from polyisocyanates with at least three isocyanate groups.
  • alkylene means a divalent radical obtained by removing two hydrogen atoms each from a non-adjacent carbon atom of an original hydrocarbon and includes alkylenes from 3 to 18 carbon atoms, including, for example, 1,3-propylene, 1,4- Butylene, 1, 5-pentylene, 1,8-octylene and 1, 10-decylene These radicals can be either branched or linear and these groups can also be substituted.
  • n are derived from the starting materials used in the reaction. These are described above. Accordingly, m is preferably equal to 1, but to increase the tear strength, polyisocyanates with three or more functionalities can also be used, so that consequently one
  • Particularly preferred urethane (meth) acrylates for the present invention have three or four reactive terminal ethylenically unsaturated functionalities.
  • the urethane (meth) acrylates preferred for the invention can be prepared by processes in which i) at least one hydroxyalkyl (meth) acrylic acid ester
  • urethane (meth) acrylates for the present invention can be prepared in a two-step synthesis.
  • equimolar amounts of hydroxyalkyl (meth) acrylic acid ester and polyisocyanate are reacted, after which the reaction product thus obtained is mixed with a suitable amount Polyoxyalkylene can react.
  • suitable polyisocyanates are selected or a suitable reaction is carried out, in particular urethane (meth) acrylates with ( three reactive terminal ethylenically unsaturated functionalities) can be obtained.
  • reaction can be carried out in bulk, i.e. be carried out without the use of another solvent. If desired, an inert solvent can also be used. These include benzene, toluene and
  • catalysts such as tertiary amines
  • these include, inter alia, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N, N-diethylcyclohexylamine and NNN ', N' tetramethyldiaminomethane, or organic tin compounds, including dibutyltin dilaurate and tin dioctoate.
  • inhibitors can be added which prevent radical polymerization of the (meth) acrylates during the reaction. These inhibitors are well known in the art.
  • Component B) is an optional component, but is used very preferably.
  • B) can be mixed as a polymeric substance with A).
  • A) can be prepolymerized, giving a so-called syrup.
  • This syrup then already contains monomeric constituents from group A) and polymeric sand particles from group B) in a mixture with one another.
  • a polymer or prepolymer B) can be added to component A).
  • This (pre) polymer should be soluble or swellable in A). 0 to 12 parts of the prepolymer B) are used for one part A).
  • Poly (meth) acrylates are particularly suitable, where they can be dissolved as a solid polymer in A) or used as so-called syrups, ie partially polymerized mixtures of corresponding monomers.
  • Polyvinyl chloride, polyvinyl acetate, polystyrene, epoxy resins, epoxy (meth) acrylates, unsaturated polyesters, polyurethanes or mixtures thereof are suitable. These polymers cause e.g. B. special flexibility properties, shrink regulation, act as a stabilizer or flow improver.
  • the (pre) polymer B) is preferably dissolved in A).
  • the weight ratio of components B) and A) of the binder is in the range from 1: 1 to 12: 1. In this range, the properties can be optimally matched.
  • Weight ratios B): A) in the range from 5: 1 to 12: 1 are particularly expedient.
  • Component B) ((pre) polymer) can be any polymer. It is particularly expedient to use a suspension polymer, emulsion polymer and / or grinding granulate from recycling processes. The average particle diameter of the (pre) polymers is then usually ⁇ 0.8 mm.
  • Prepolymer B) is very advantageously a PMMA varnish bead obtainable by suspension polymerization. This can make single-layer semifinished products possible, in particular with sufficient impact strength of the resulting shaped bodies.
  • the average particle diameter of the paint bead is about 0.1-0.8 mm. 0.2-0.8 mm, in particular 0.4-0.8 mm, are preferred.
  • the (pre) polymer B) is preferably a copolymer, the hardness and flexibility of the reinforcing layers being influenced by the type and amount of the comonomer in the (pre) polymer B).
  • Suitable comonomers which are involved in the structure of the (pre) polymer B) include, inter alia, acrylates and methacrylates which are different from methyl methacrylate (MMA), vinyl esters, vinyl chloride, vinylidene chloride, styrene, - methylstyrene and the various halogen-substituted styrenes, vinyl and isopropenyl ether, dienes, such as 1,3-butadiene and divinylbenzene.
  • MMA methyl methacrylate
  • Preferred comonomers are for methyl acrylate and the like. a., ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl ethacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, propyl acrylate, propyl methacrylate, methacrylic acid, ethyl triglycol methacrylate, hydroxypropyl methacrylate.
  • Component C) is an essential component that is indispensable for curing (polymerization) the polymerizable system.
  • the polymerization can be free-radical or ionic, with free-radical polymerization being preferred. It can be carried out thermally, by blasting and by initiators, preferably initiators which form free radicals being used.
  • initiators preferably initiators which form free radicals being used.
  • Polymerization depends on the monomers chosen and the initiator system and are well known in the art.
  • the preferred initiators include, among others, the azo initiators well known in the art, such as AIBN or 1, 1-azobiscyclohexane carbonitrile, and
  • Peroxy compounds such as methyl ethyl ketone peroxide
  • Redox systems are also suitable, and desensitized systems in organic solvents or in aqueous solutions or in aqueous suspension are also known and can be used. Such a system is available under the ® Cadox brand from Akzo.
  • the amount of component C) is variable within wide limits. It depends on the composition of the monomers, the type and amount of the (pre) polymer and the desired polymerization temperature and the desired molecular weight of the polymer to be prepared. Standard values arise, for example for molecular weights of 10,000 to 200,000 (weight average molecular weight) to 2xl0 "5 to about IxlO -4 moles initiator per mole of polymerizable components of the monomer system. Depending on the molecular weight of the initiator compound (s) used per come Part by weight of component A) about IxlO -3 to 5xl0 "5 parts by weight of component C) in question
  • Component D) is an optional component of the polymerizable (meth) acrylate system, but is preferably contained in the system.
  • examples are emulsifiers. Lecithins are preferred.
  • the amount of substances to be used can be varied over a wide range. 0.01 to 1 part by weight of D) per 1 part by weight of A) are preferred. 0.1 to 0.2 part by weight D) per 1 part by weight A) are particularly useful.
  • Component E) is optional. These are the usual additives which are known per se, exemplary additives having been listed above.
  • E) includes fillers that do not fall under F). This therefore includes fillers which do not have a reinforcing action, such as color pigments and the like, which are particularly preferably of smaller particle size than the fillers of component F).
  • the average particle size of the fillers used according to E) is preferably in the range of less than 10 ⁇ m, advantageously in the range of less than 5 ⁇ m, particularly preferably less than 1 ⁇ m and very particularly preferably less than 0.01 ⁇ m.
  • the ratio of the average particle sizes of the fillers E) to F) is advantageously in the range from 1: 3 to 1: 1000, preferably in the range from 1: 5 to 1: 100 and particularly preferably in the range from 1:10 to 1:50.
  • Component F is essential. In addition, this component has been previously described in detail.
  • Moldings can be obtained from the semifinished sheet according to the invention by shaping processes known per se.
  • the poly (meth) acrylate plate is firmly clamped at the edge of the mold, after which the molded part is removed from the heated, free blank by forming forces. brings the desired shape.
  • the forming forces include vacuum, compressed air or mechanical forces, e.g. Pre-stretching stamp or hold-down, which can be used individually or in combination.
  • the wall thickness of the poly (meth) acrylate plate decreases.
  • the poly (meth) acrylate plate is preferably heated to a temperature in the range from 140 to 210 ° C., particularly preferably 170 to 190 ° C.
  • the shaping devices usually also have a heating device which heats the plate, for example by infrared rays, air or by contact, heating by infrared being preferred, since this method heats the plate uniformly but also only specifically and selectively heats it Areas of the plate.
  • the heated plate is then pulled into the mold. This is done with the help of the above-mentioned forming forces, the area between the plate and the mold being vented by vacuum in most of the embodiments of thermoforming devices.
  • Two sekurit glass plates are used as a mold.
  • a PVC sealing cord is placed between the molded glass plates.
  • the glass plates are then fixed on three sides using clips.
  • the width of the chamber can be varied by different thicknesses of the sealing cord. In the example, the inside thickness of the chamber was about 8 mm.
  • the fourth side is closed after filling.
  • the plate system sealed in this way is stored horizontally and placed in a water bath.
  • prepolymer is a syrup based on MMA, in which methyl methacrylate has been prepolymerized in a known manner up to a conversion of about 10% (90% by weight of residual monomer).
  • the viscosity of the prepolymer was about 450 cp.
  • Aerosol OT is a diocyl sodium sulfosuccinate from Cyanamid and is used as a release agent / mold release agent.
  • Soy Lecithin is a product of Stern Lecithin and Soja GmbH and is called
  • Color paste is a name for a mixture consisting essentially of titanium dioxide, colored pigments and dioctyl phthalate (DOP). The mixture becomes
  • Tinuvin 770 is the company's light stabilizer
  • Ciba - Specialty Chemicals GmbH and belongs to the group of HALS products.
  • the semi-finished product from 1.3. has a thickness of about 8 mm.
  • An approximately 1.5 x 1.5 m semi-finished product is deep-drawn into a shower base. This is done as follows: The plate to be deformed is fixed in a metal frame. On the top and
  • the underside of the plate is heated with infrared radiators until a surface temperature of approx. 190 ° C is reached.
  • the infrared radiators are then removed and a mold is brought up to the underside of the plate so that it is airtight with the plate.
  • the heated plate is drawn into the mold with a vacuum. After cooling, the deformed body can be removed.
  • Lecithin stands for soy lecithin.
  • Plastorit Super is a 3-component mineral from Naintsch, Austria. It is a platelet-shaped intergrowth of the minerals mica, chlorite and quartz with the chemical, physical data: Si02: 58.0%, A1203: 20.0%, MgO: 12.0%, FeO: 3.0% and K20 :
  • the residue is 2% to 12 ⁇ m.
  • the grain distribution has a 50% value at about 3 to 4 ⁇ m, the 90% value is at about 8 to 9 ⁇ m.
  • the shower base according to Comparative Example 5 had no high-gloss surface.
  • the shower bases according to Examples 1 to 4 met the requirements of the relevant standards. In particular, the following tests were carried out and passed, for example, on the shower base according to Example 3:

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PCT/EP2001/000489 2000-02-03 2001-01-17 Selbstverstärkendes, thermoplastisch verformbares halbzeug, insbesondere für die herstellung von sanitärartikeln, verfahren zur herstellung sowie daraus hergestellte formkörper WO2001057117A1 (de)

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EP01909640A EP1210385B1 (de) 2000-02-03 2001-01-17 Selbstverstärkendes, thermoplastisch verformbares halbzeug, insbesondere für die herstellung von sanitärartikeln, verfahren zur herstellung sowie daraus hergestellte formkörper
AU37310/01A AU3731001A (en) 2000-02-03 2001-01-17 Self-reinforcing thermoplastically-deformable semi-finished product, in particular for the production of sanitary items, method for production thereof and moulded bodies made therefrom
US09/926,249 US6699544B2 (en) 2000-02-03 2001-01-17 Self-reinforced shaped article
DE50109287T DE50109287D1 (de) 2000-02-03 2001-01-17 Selbstverstärkendes, thermoplastisch verformbares halbzeug, insbesondere für die herstellung von sanitärartikeln, verfahren zur herstellung sowie daraus hergestellte formkörper
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008122428A1 (de) * 2007-04-05 2008-10-16 Scheer Surface Solutions Gmbh Kunststoffformteile und ihre herstellung
EP2011425A1 (en) * 2007-07-05 2009-01-07 TEUCO GUZZINI S.p.A. A shower tray, an assembly kit thereof and an installation method for the shower tray itself
EP3401087A1 (de) * 2017-05-08 2018-11-14 Falko Mauersberger Herstellung einer acrylwanne mit rutschhemmender oberfläche

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10125571A1 (de) * 2001-05-25 2002-12-05 Ticona Gmbh Mischungen mit hoher Diversität, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10238992A1 (de) * 2002-08-20 2004-02-26 Röhm GmbH & Co. KG Lärmschutzplatte aus Acrylglas
DE10254276A1 (de) * 2002-11-20 2004-06-03 Röhm GmbH & Co. KG Verfahren zur Herstellung einer Kunststoff-Platte mit schichtförmigem Aufbau
DE102004055365A1 (de) * 2004-11-04 2006-05-11 Schock Gmbh Kunststoff-Formkörper und Verfahren zu dessen Herstellung
ES2525199T3 (es) * 2009-07-16 2014-12-18 Evonik Röhm Gmbh Agente aglutinante para la producción de marcaciones de calzadas por encima de las que se puede rodar con rapidez
ITBS20120155A1 (it) * 2012-10-31 2014-05-01 Insab S P A Articolo di arredo bagno
CN104665667B (zh) * 2013-12-03 2017-05-03 常州市维益科技有限公司 亚克力浴缸的制作工艺
TR201700918A2 (tr) * 2017-01-20 2018-07-23 Seranit Granit Seramik Sanayi Ve Ticaret Anonim Sirketi Eği̇mli̇ serami̇k duş karosu
US11485094B2 (en) * 2018-05-18 2022-11-01 Polysto Process for the production of an article for the cladding of floors or walls

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734828A1 (en) * 1995-03-27 1996-10-02 Atohaas Holding C.V. Process for producing a thermoformable acrylic resin sheet, thermoformable acrylic resin sheet and shaped article having a granit-like appearance which has been obtained by thermoforming such a sheet

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4085246A (en) * 1975-06-18 1978-04-18 E. I. Du Pont De Nemours And Company Simulated granite and its preparation
DE2861961D1 (en) * 1977-11-14 1982-09-09 Ici Plc Decorative acrylic sheets and articles formed therefrom
JPS59217664A (ja) * 1983-05-20 1984-12-07 旭化成株式会社 人工大理石の製造方法
JPS61171713A (ja) * 1985-01-25 1986-08-02 Kyowa Gas Chem Ind Co Ltd ポリメチルメタクリレ−ト系成型品の製造方法
JPH04254456A (ja) * 1991-02-07 1992-09-09 Yamaha Corp 人工大理石及びその製造方法
US5756577A (en) * 1995-03-27 1998-05-26 Grupo Cydsa, S.A. De C.V. Styrene butadiene copolymer and polyolefin resins based shrink films
EP0847852A3 (de) * 1996-12-10 2004-03-03 Basf Aktiengesellschaft Verbundschichtplatten oder -folien und Formkörper daraus

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734828A1 (en) * 1995-03-27 1996-10-02 Atohaas Holding C.V. Process for producing a thermoformable acrylic resin sheet, thermoformable acrylic resin sheet and shaped article having a granit-like appearance which has been obtained by thermoforming such a sheet

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008122428A1 (de) * 2007-04-05 2008-10-16 Scheer Surface Solutions Gmbh Kunststoffformteile und ihre herstellung
EP2011425A1 (en) * 2007-07-05 2009-01-07 TEUCO GUZZINI S.p.A. A shower tray, an assembly kit thereof and an installation method for the shower tray itself
EP3401087A1 (de) * 2017-05-08 2018-11-14 Falko Mauersberger Herstellung einer acrylwanne mit rutschhemmender oberfläche

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DE10004452A1 (de) 2001-08-09
DE50109287D1 (de) 2006-05-11
US20030017289A1 (en) 2003-01-23
JP2003522240A (ja) 2003-07-22
AU3731001A (en) 2001-08-14
CN1362974A (zh) 2002-08-07
KR100797806B1 (ko) 2008-01-24
PL350034A1 (en) 2002-10-21
US6699544B2 (en) 2004-03-02
CZ20013539A3 (cs) 2002-05-15
EP1210385B1 (de) 2006-03-22
EP1210385A1 (de) 2002-06-05
CN101265336A (zh) 2008-09-17
ATE321092T1 (de) 2006-04-15
KR20020005641A (ko) 2002-01-17
PL200266B1 (pl) 2008-12-31

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